Catalytic conversion process



Oct. 27, i942. B. L. EVERING ETAL CATALYTIC CONVERSION PROCESS Filed Oct. 14, 1940 2 Shee'LS--Shee'tl l www@ Q\ umw NNW 550% .www w@ WS @s w@ 2 Sheets-Sheet 2 m Q @Ng B. l.. EVERING ET AL CATALYTIC CONVERSION PROCESS Filed ct. 14, 1940 Oct.' 27, 1942.

Patented oef. 21, 1942 CATALYTIC CONVERSION PROCESS Bernard L. Evering and Edmond L. dOuville, Chicago, Ill., assignors to S Chicago, Ill., a corporati tandard Oil Company, on of Indiana Application october 14, 1940, serial No. 361,022 s claims. (c1. 19e-vs) 'I'his invention relates to thecatalytic conversion of hydrocarbons and more particularly to a process for the conversion of hydrocarbons involving the use of an active aluminum halide catalyst. Still more specifically, it relates to -a conversion process of lyst is an active liquid aluminum halide-hydro- -carbon complex having an exceptionally long life.

It is well-known that the branched-chain paramn hydrocarbons and naphthas containing them in substantial proportions are very valuable as motor fuels and particularly as airplane fuels because of their high antiknock values. freedom from gum-forming tendencies and high heat content per proposed to produce such naphthas from substantially saturated liquid fractions which are rich in straight-chain paraiiin hydrocarbons by the action of aluminum chloride or other active aluminum halide catalysts in the presence of an activator such as hydrogen chloride, and we have described a particularly advantageous process of this type in our co-pending application Serial No. 308,480, led December 9, 1S 39, of which this application is a continuation-impart.

In carrying out the conversion of straightchain paraflin hydrocarbons to branched-chain paraffin hydrocarbons on a refinery scale it is extremely advantageous that the process be co tinuous and this fact makes it very desirable to have the catalystin liquid form, so that it can be pumped readily through pipes, tubes and other apparatus. It has, of course, long been known that aluminum chloride in the presence of a hydrocarbon such as an olefinic or. aromatic hydrocarbon under conversion conditions will gradually, and sometimes very rapidly, be converted into an aluminum chloride-hydrocarbon complex which is a liquid and retains a portion of the activity of the original aluminum chloride. However, such complexes are rapidly degraded under the usual reaction conditions to an inactive sludge and this degradation has been a major factor in limiting the commercial use of aluminum chloride in hydrocarbon conversion processes.

We have found that hydrocarbon conversion processes, .and particularly the production of branched chain paraffin hydrocarbons from this type in which the catastraight-chain paraiiin hydrocarbons can be carried out most effectively in the presence of an active liquid aluminum halide-hydrocarbon complex produced by the action of an aluminum halide such as anhydrous aluminum chloride on highly branched paraiiln hydrocarbons in the presence of an activator such as hydrogen chlo ride at a relatively low temperature, and that such complexes exhibit the unexpected property unit Weight of fuel. It has been of increasing in activity with use.

It is an object of our invention to provide an economical hydrocarbon conversion process particularly adapted to the production of high antiknock mptor vfuel fractions in vthe presence of an unusually effective liquid aluminum halide catalyst. Another object is to provide a process whereby naphthas having low antiknock values due to their content of straight-chain parailin hydrocarbons are converted into high antiknock motor fuel fractions in the presence of an active aluminum halide catalyst derived from highly branched paraffin hydrocarbons. A still further object is to provide a continuous process of the type described in which the naphtha to be converted and a liquid aluminum halide-hydrocarbon complex catalyst are continuously and concurrently passed through an elongated reaction zone. Other objects, advantages and uses of our invention will appear from thel description thereof read in conjunction with the drawings, which form a part of this specification, and in which:

Figure 1 shows in a schematic manner an ap- -paratussuitable'for carryingv out our invention,

and

Figure 2 is a graph of the results obtained in comparable experiments demonstrating in part the advantages derived' from operating in accordance with our invention.

The active liquid aluminum halide-hydrocarbon complex utilized in accordance with our invention is prepared by the action of an -aluminum halide catalyst, such as anhydrous aluminum chloridev or aluminum bromide, and` an activatoraffording a hydrogen halide on a substantially saturated fraction containing predomat least two side chains at a temperature in the range from about 50 F. to about 175 F. Preferably this liquid catalyst complex in prepared following detailed one paraflin hydrocarbon having quantities crise-octane.

,/'naphtha rich in straight-chain l, `largely .in the' liquid phase.

tions are for example` the hydrogenated polymers and co-polymers Ofoleflns having vlcjssv than Vsix carbon atoms per molecule, namely, ethylene, propylene and the, products of alkylation of isobutane and of isopentane with oleiins of the class described. These fractions are very rich in highly branched parainhydrocarbons, lthe hydrogenated polymers of isobutylene, so-called iso-octane v(2,2,4#-trimethylpentane).

While certain alkylation products also contain this and other similar hydrocarbons, we prefer for example,l being richin and a" frction'iicniiibranchedfehamfpramn the butylenesV and amylenes," and fuel fraction is separated fromthe products( Y feroce l from 'aluminum chloride and a substantially sat- "i urated fraction containing paraln hydrocarbons having `at leastV sixcarb'on atomsfandftwo side chainsper molecule.. Suitable saturated frachydrocarbons comprising? a high antiknock motor This process isreferred to herein as isomeriza tion, although some changes in molecular weight occurpsimultaneously withthe molecular rear- 'I he feed stockto our isomerization processcan be any substantially saturated naphthaV rich in straight-chain paramn hydrocarbons. For example, it can be a relatively pure, normally liquid c straight-chain paraln hydrocarbon such as nor.

mal pent'ananormal hexane or normal heptanep,l

but generally predominantly straight-'run naphto prepare our complex from a fraction rich in iso-octane, although less volatile fractions rich in hydrogenated trimers and mers of isobutylene are also eifective in producing the desired complex.

In one case an aluminum at atmospheric pressure a quantity ofanhydrous aluminum chloride with an excess of commercial viso-octane at 120 F. to 140 F. until a liquid complex resulted. Y During the complex formation large amounts of isobutane'were produced and the remaining hydrocarbon liquid contained 50% of material boiling` is suitable lfor safety fuel while the isobutane 'can be utilized readily in an alkylation process, for example. The complex itself vcan be decanted from theunreacted' aluminum chloride, which can be ultimately converted in its entirety tothe complex by further treatment with additional complex catalyst produced wasless than that of S. A. lil.l 50 lubricating oil and it could be easily pumped through pipe s, `contacting equipment. A complex catalyst prepared by the vaction yof anhydrous aluminum even heavier poly higher than the endpoint of the original iso-octane. This heavy materialthas such as lthose from Michigan, Pennsylvania -or Mid-Continent crude oil are preferred since they are much more readily available.` Another excellent feed stock is the highly parafnic naph# chloride-hydrocab' bon complex was prepared by stirring together4 tha produced bythe FischerfTropsch process from Natural gasocarbon monoxide and hydrogen. line fractions and so-called distillates" are also suitable and are plentiful vand inexpensive in some production areas. Itis very important' that the feed stock be free or almost free fromaromatic hydrocarbons'since they have been found to reduce the activity of the v catalyst to a very marked -l degree, andconsequently to limit seriously they amount of conversion obtained per unit weight of catalyst. Our -preferred feedA stocktherefore contains less thanabout 5%i and preferably' 0.5- 1.0% or less of aromatic hydrocarbons. In many cases `a' preliminary solvent extraction' sterorA other treatment is necessary or desirable to'rekduce'the aromatic content of the'feed. Oleiinic hydrocarbons are also undesirable'and 'should not be present in more thanv very .sinall' amounts.

- while'cyclo-paraiinic or naphthenic'hydrocarbons 'can be tolerated in 'considerable quantities.

. Nevertheless, the feed stock should preferably towers :or any form of chloride on a lightv naphtha fraction rich in straight-chain paraiiin other hand, at a temperature above 200 F.,.wh1ch hydrocarbons," on the initiall boiling pointl as low as about 30? F. and

is necessary in order that the complexmay be' i formed in a reasonable time, was much less iuid.v

As be shown hereinafter, the activity ofthe complex Vprepared from iso-octane increased very markedlywith *use while thatfrom the'light naphtha gradually declined.

` The active liquid aluminum halide-hydrocarbon complex-is particularly luseful yin reactions involving' the production of branched-chain from straight-champaraiiin hydrocarbons, although it can also be used in the alkylation of isobutane or isopentane with normally under suitable conditions. In one of its most im' portant aspects ourinventioncomprises contact' ing an admixture of-a' substantially saturated paraffin hydrocarbons, an active liquid aluminum halide-hydrocarbon complex prepared from a highly branchedparafn hydrocarbon as described above and an activator affording a hydrogen halide urider the` reaction conditions lin a reaction zone i e maintained at atemperature'in the range from about 100" F. to about 450 F. and a superatmosrpheric pressure sufcient to maintain the naphtha tions a largey proportion fof the straightchain paraffin hydrocarbons in verted to branchedfchain paraflin :hydrocarbons contain at least %`l of 'paraffin hydrocarbons and those containing at least 80% of paraffin hydrocarbons are especially desirable. j

In general'the naphtha feedstock shouldv have a boiling range Within the'range from about100" F. to abouti 500 F., althoughnaphthashavingjan including about 25% io 30%v by-weightbffbiitgiies may b e used. A particularly suitable naphtha feed-is one prepared by the 'distillatio'nand 'fractionation of a; straight-run or natural gasoline stock to produce a light naphtha having an initial boilingv point in therangeffrom about 30.F.`to about 90 F. or higher and an end point in the aromaticihydrocarbons and most of the naph range from about 145 F.to about 158 F preferably about 152 F. Substantially all of the thenic hydrocarbons such .as cyclohexane are exgaseousolefins and for the catalytic polymerization of such oleflnsl cluded from this fraction and it is very richvin straight-chain 'paraffin hydrocarbons. Under special circumstances it may be desirable to `use alight 'naphtha fraction boiling within a still .narrower range.

.The concentration, of aluminum halide-hydrocarbon Vcomplex catalyst present in the reaction Under these condithe naphtha are conf j zone' can vary within wide `limits depending pri- -marilyupon the-temperature, reaction time and time v The activator supplied to the reaction zone is a substance aiording a hydrogen halide under the conditions prevailing therein, which can be either a hydrogen halide itself such as hydrogen chloride or hydrogen bromide, or it can be carbon tetrachloride or one of the alkyl halides such as methyl chloride or bromide, ethyl chloride or bromide, etc. In general, the chlorinated and brominated hydrocarbons, particularly the more volatile ones, are suitable, and even water can be used since a hydrogen halide will be generated therefrom by reaction with the catalyst, but this is not preferred since the catalyst is thus deactivated more rapidly than would otherwise be the case. Preferably the amount of activator used is sufllcient to supply a concentration in the reaction zone of about 1 to 2 mols of hydrogen halide per mol of aluminum halide, which will usually be in the range from about 0.1 to about 15.0% by weight, based on the reacting hydrocarbons present. The activator used in the preparation of the complex catalyst can be any of those indicated above, with the exception of water, which is undesirable for the reasons pointed out. Hydrogen chloride, however, is the preferred Aactivator in all cases because of its availability and low cost.

The isomerization reaction is preferably carried out in the presence of free hydrogen, as disclosed in our application Serial No. 308,480, for the reason that the hydrogen greatly assists in increasing the yield of valuable hydrocarbon products per unit weight of catalyst. In this case the hydrogen is supplied under a pressure in the range from about 250 to about 3000 pounds per square inch and preferably at a pressure in the range from about 500 to about 1500 pounds per square inch. Relatively pure hydrogen is, of course, particularly suitable but in the plant operation of our process hydrogen containing impurities such as methane is available at much lower cost and can be used effectively as long as the hydrogen content of the gas is above about 50 mol per cent, in which case the hydrogen pressure previously mentioned would be the hydrogen partial pressure rather than the total gas pressure. It is also preferred that the hydrogen should be largely dissolved in the naphtha, particularly when our process is operated on a continuous basis. Generally the amount of free hydrogen present is less than about volumes of gaseous hydrogen measured at 60 F. per volume of liquid naphtha and preferably it lies in the range from about 10 to 25 volumes of hydrogen per volume of naphtha, although under some circumstances smaller amounts can be used.

' Another important variable which influences the course of the reaction is temperature. In general temperatures ranging from about 100 F. to about 450 F. are suitable, although different reaction times and amounts of catalyst are almost imperative in order that economically practicable results may be obtained at various temperatures. Usually we prefer to carry out the reaction in the range from about 200 F. to about 350 F. in order that it may proceed rapidly and without drastic over-treatment. In ,the upper portion of the broad temperature range specified the tendency toward decomposition into normally gaseous hydrocarbons such as isobutane can be inhibited by supplying a relatively small quantity of one of the butanes to the reaction zone.

. It is apparent that the isomerization process above described can be carried out either batchwise or continuously, although we greatly prefer continuous concurrent flow of the naphtha feed and the active liquid aluminum halide catalyst. Certain portions of the apparatus must obviously be constructed of corrosion-resistant material to prevent rapid deterioration thereof from active halogen compounds present. Many suitable types of apparatus can be designed readily by one skilled in the art, but our invention will be described in detail in connection with only one of these, as illustrated in Figure 1, to which reference is now made.

'I'he naphtha feed is introduced into the system by means of pump I0 and line II and passes into a chamber I2 in whichit is mixed with a gaseous activator such as hydrogen chloride supplied by pump I3 through line I4. In the arrangement shown only that portion of the activator which dissolves in the naphtha is allowed to escape from chamber I2 and in the case of hydrogen chloride this the following data on the solubility of hydrogen chloride in a light naphtha at various temperalures and pressures:

Table I B Cl pressure However, the activator can be mixed directly with the feed stock or otherwise introduced into the system and these methods are, of course, used in connection with normally liquid activators. When very high pressures are to be used in carrying out the isomerization reaction the pressure in chamber I2 is preferably maintained in an intermediate range, for instance, 200 to 300 pounds per square inch or less. This pressure is controlled so as to supply enough activator to give thedesired concentration when considered with the activator in th recycle streams described below.

` The naphtha now containing dissolved activator is' passed through pump I5 and lines I6 and I'I into a reaction zone I8 which, as shown, is a heated elongated coil I9 maintained at the desired reaction temperature. A pressure vessel,

` including stirring equipment may be substituted for reaction zone I8 but the form shown or a modication thereof using heat exchange with steam, diphenyl or other heat-transferring fluid, is preferred for continuous operation. In order to maintain the necessary agitation between the catalyst and the other reactants it is necessary that the velocity through coil I9 shall be great enough to insure turbulent flow. Knothole mixers or other baille arrangements may be inserted in coil I9 at several places to aid in achieving this result. The liquid aluminum halide-hydrocarbon complex prepared as hereinabove specified is supplied to line I'I and mixed therein with the feed stock by means of pump 20 and lines 2l and 22, and when hydrogen is used, as We prefer,

is sufficient, as shown by it is likewise introduced intoline I1 through compresser 23 and lines 24 and 25.

The entire reaction mixture. passes through line 26 and cooler 21 to a separator 28 in which the valuminum halide-hydro-v carbon complex settles out as a lower layer and is continuously withdrawn through line 29. This complex or a major portion thereof is preferably recycled to line I1 through valve 30, line 3I,' v pump 32 and line 22.

or a portion thereof can be treated with water or otherwise to furnish hydrogen halide forA use as activator in the process.

The remainder of thefproducts from coil I8 consists essentially of free hydrogen, if that sub-v stance has been supplied to the reaction, hydrogen halide, naphtha rich in branched-chain paraffin hydrocarbons and possibly some normally gaseous paraffms such as isobutane formed during the reaction. These are allowed to stratify in separator 28 so that a gaseous phase forms above the liquid hydrocarbon layer. When hydrogenhas been used the pressure within separator 28 is preferably maintained as close as possible to the reaction pressure existing within coil I9, although it is obvious that there will be some pressure dropin transferring the reactants from coil I9 to separator 28. In this case the temperature of separation depends to a very conturned to the reaction zone I8 by means of line 35, pump 36, line 25 and line I1. If hydrogen Ahas not been used, however, the pressure in separator 28 is preferably substantiallyl reduced and the temperature is maintained at a somewhat higher value so that the gas recycled through line 35 will consist essentially of gaseous paraflns.

such as isobutane, togetherwith some activator.

The hydrocarbon layer is removed-from separator 28 through line 31 and valve 38 and iiitroduced into fractionating tower 39 through a heater 40. Valve 38 is. preferably ofthe pressure-reducing type adjusted tothe desired fractionating pressure. Fractionating tower 39 can `from con la This hydrogen-rich gas isr Withdrawn from the top of separator 28 and re-V w 2,soo,24o atoms per molecule -and possibly additional-free` f hydrogen and some hydrogen halide, iswithdrawnas an overhead through line 50. This gaseous fraction is preferably recycled to line I1 `through valve I, line 52,pump 53-and'line 54. In order that inert gases may be prevented from accumulating in the system, however,a portion vintermittently or continuously through valve 55 and line 56. In that case free hydrogen and/ or hydrogen halide' lcan. be recovered from vent of the material in line 50 may be vented either gases. Alternatively, the hydrogen halide can l 'be removed from the products by a'caustic washv ing step `or the like prior to their' introduction Y into heater 40 and fractionating tower'39.

` As previously mentioned. small amounts ofI Y normal butane or isobutanev can be supplied to reaction zone I8when'the reaction temperature is relatively, high, for instance,l 300 F. to 450 F.

and this'can .bedoneby means of pump 51line 58, valve 59 and lines 54 and I1. Generally, however, this expedient willbe unnecessary when operation has been carried out for a period of time since suilcient isobutane will be formed and recycled through line 35 and/or line 52 to act as an inhibitor effectivein suppressing the formation of further quantities of isobutane.

It is apparent from the above that we have described a novel method of .isomerzing parafnic naphthas to produce high antiknock motor fuel fractions bythe use of a liquid aluminum halide-hydrocarbon complex which isparticularlyadapted to continuous plant operation.

siderable extent upon the character of the feed y determine the effectiveness of catalysts of thisl type.` In Run 1 the particular catalyst used Was perimental conditions.

be of any conventionaldesign and, as shown, is provided with aside stream outlet 4l for the` will contain considerable amounts of unconf verted naphtha andare recycled to the. reaction zone I8 through line 42,v valve 43, line 44, pump 45, valve 48 and lines I8 and I1. If substantially all of the material boiling in the motor fuel range is Withdrawn Aas a side stream, however, the relatively heavy bottom fraction may be withdrawn from the system throughvalve 41;

and line 48, although this also 'can be recycled.

In orderto illustrate the unusual property ofV the aluminum halide-hydrocarbon complex catalysts prepared as already described an experiment was carried out, herein called fRun 1. to

prepared by the action of anhydrous aluminum chloride and hydrogen chloride at atmospheric pressure and about 120 F. to 140 F. oncommercial iso-octane, which is a product vconsisting essentially of the hydrogenated polymers and co-polymers of the butylenes.` Since no continuous "apparatus wasl available a number of successive tests were made under typical conditions', using the same .charge of catalyst, the

length of each test being determined by the time in which the bomb pressure dropped a predetermined amount, since it had been'previously noticed that this was related. to the extent of octane number improvement of. the naphtha feed, although the proper reaction timecannot be determined accurately in all cases under lex- In this experiment the naphthafeed was a samplevof light virgin naphtha derived from Mid-Continent'crude oilboiling-V between 110 F. and 153 F. and having an octane number of 67.5y (CFR-M). 'The pertinent data for Run l areshown in Table II. It .will

be noted that inv the first six portions of this run the amount of aluminum chloride iny the vcatalyst was 98.5 gms., whereas thereafter it was 74.5 gms. f -This reduction in the amount of catalystl-was due. to theffact that itv lwas at first vthought that theamount ofv aluminum chloride in the complex was about 45%'1wh`ereas itwas The desired product inline 4I is passed through4 actually 62.6%., asdiscovered by ,subsequent analysis, and the amountof complex was therefore reduced during Run 1 tomake it correspond more nearly to';Run 2 described below. vHowever,A perusalV of 'the data ywill lindicate clearly thatthe activityof thev vcatalyst increases very Vmarkedly with use.

temperature in ght-chain parafn prises contacting in a F. to about 450 F; and

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a pressure in the range from about 250 to about 3000 pounds per square inch an admixture of said naphtha, an activator affording a hydrogen halide and an active liquid aluminum halide-hydrocarbon complex preparedby the action of an aluminum halide catalyst and-an activator affording a hydrogen halide on a substantially saturated fraction. containing predominantly at least onevparamn hydrocarbon having at least two side chains at a temperature in the range from about 50 F. to about 175 F., removing the products from said reaction zone, andseparating said high antiknock motor fuel fraction from said products. l

2. The process in claim 1 wherein said active liquid complex is preparedA from a substantially saturated fraction containing hydrocarbons having at least six carbon atoms per molecule. selected from the group consisting of hydrogenated polymers and copolymers of' oleflns having less than six carbon atoms per molecule, and the products of alkylation of-.isobutane and of isopentane with uoleins having less than six carbon atoms per molecule.

3.' The process of claim l wherein said substantially saturated fraction is rich in hydrogen- 'ated polymers of isobutylene.

4. The process of claim l wherein the temi perature in said reaction zone is in the range` from about 200 F, to about 350 F.

5. The process of claim 1 wherein said aluminum ,halide catalyst is aluminum'chloride and chain paran hydrocarbons, the step comprising passing an admixture of said naphtha, an activator aording a hydrogen halide and an active liquid aluminum chloride hydrocarbon comportion.

plex through an elongated reaction zone maintained at a temperature in the range from about 100 F. to about 450 F. and a superatmospheric pressure sufficient to maintain said naphtha substantially in the liquid phase, said complex being prepared by the action oi' anhydrous aluminum chloride and an activator affording a hydrogen halide on a substantially saturated fraction rich in at least one parailin hydrocarbon having at least two side chains and at least six carbon atoms per molecule at a temperature in the range from about F. to about 175v F.

-7. The process of claim 6 including the additional steps of removing'the products from said reaction zone, separating aluminum chloride-hydrocarbon complex from said products, and recycling at least a portion of said separated complex to said reaction zone.

8'. In a continuous process for producing a high antiknock motor fuel fraction from a substantially saturated naphtha rich in straightchain paraln hydrocarbons, the steps comprising passingy an admixture of said naphtha, an active liquid aluminum chloride-hydrocarbon complex, hydrogen chloride and free hydrogen through an elongated reaction zone maintained at a temperature in the range from about 200 F. to about 350 F. and under apressure in the range from about 250 to about 3000 pounds per square inch, said complex being prepared by the action of anhydrous aluminum chloride and hydrogen chloride on a substantially saturated fraction rich in iso-octane at a temperature in the range from about 75 F. to about 150 F.,

separating .a 'hydrocarbon-containing portionv from saidproducts and recovering said motor fuel fraction from said, hydrocarbon-containing BERNARD L. EVERING.

mii/rom) L. n'oUvILLE. 

